2856 Ind. Eng. Chem. Res.

2006, 45, 2856-2861

Estimation of the Normal Boiling Point of Organic Compounds

Ritesh Sanghvi* and Samuel H. Yalkowsky
College of Pharmacy, The UniVersity of Arizona, Tucson, Arizona 85721

A semiempirical model has been developed for the estimation of the normal boiling points of organic
compounds. The normal boiling point is calculated as the ratio of the enthalpy of boiling to the entropy of
boiling. Both these values are estimated independently using a combination of additive group contribution
and nonadditive molecular descriptors. A group contribution model is proposed for the estimation of the
enthalpy of boiling, based on the experimental data for 1322 structurally diverse organic compounds. The
average absolute error associated with this estimation is 0.83 kJ/mol. A semiempirical model has been developed
for the estimation of the entropy of boiling using experimental entropy data for the entire set. This model is
a modification of Trouton’s rule and takes into account the effect of hydrogen bonding and molecular flexibility.
The average absolute error associated with this estimation is 4.7 J/(K mol). The average absolute error associated
with the estimation of the normal boiling point, calculated as a ratio of the enthalpy of boiling to the entropy
of boiling, for the entire data set is 9.3 K (2.3%). A good correlation is observed between the estimated and
the experimental boiling points with an r2 of 0.98. This model is easy to use, accurate, and applicable to a
wide variety of organic compounds.

Introduction on a neural network. Basak et al.13 proposed a model using

Knowledge of physicochemical properties of organic com-
pounds is essential for predicting their behavior. The normal
boiling point (Tb), the entropy of boiling (∆Sb), and the enthalpy
of boiling (∆Hb) are important examples of such physical
properties. Besides being indicators of the physical state of the
compound, Tb and ∆Hb provide information about volatility,
i.e., its vapor pressure,1 and, consequently, its air-water and
air-octanol partition coefficients. Since these properties are
determinants of the loss due to evaporation and inhalation
exposure, they are important in both pharmaceutical and
environmental fields. Boiling point has also been used to
calculate or estimate other physical properties, such as critical
temperature,2 flash point,3 molar volume,4 and chromatographic
retention index.5
The normal boiling point and the enthalpy of boiling can be
either measured experimentally or estimated using mathematical
models. The experimental measurements are generally accurate
for pure organic compounds. A large amount of experimental
data are readily available in the literature. However, lots of
inconsistencies have been noticed6 in the literature values. The
presence of impurity or thermal instability of some compounds
may thwart the experimental measurements. In such conditions,
mathematical models can be used to provide a reasonable
estimate of these properties. Such models provide an important
tool to save time and material costs. They also provide a means
of predicting the properties of yet-to-be-synthesized compounds,
which may be very important in screening processes at a very
early stage. These reasons support the need for the estimation
of these properties.
Various methods for the estimation of Tb, ∆Hb, and ∆Sb have
been proposed. Dearden7 reviewed some of these methods.
Among the methods based on group contribution approach are
those by Joback and Reid,8 Constantinou and Gani,9 Stein and
Brown,10 and Nannoolal et al.11 Most of these models use a
multitier group contribution approach. Wessel and Jurs12 have
reported a model for predicting the Tb of hydrocarbons based
* Corresponding author. E-mail: rsanghvi@pharmacy.arizona.edu.
Tel.: (520) 626-4308. Fax: (520) 626-4063.
10.1021/ie051277g CCC: $33.50 © 2006 American Chemical Society
Published on Web 03/15/2006
topological, topochemical, and geometric parameters. Group
contribution methods have also been proposed to estimate
∆Hb.10,14 The entropy of boiling is mostly assumed to be
constant and approximated by Trouton’s rule. Recently, Kolska
et al. have proposed a new group contribution model to estimate
∆Sb.14
In this work, we have developed a semiempirical model for
the estimation of Tb. This model is based on a single-tier group
contribution approach for the estimation of ∆Hb and a modified
Trouton’s rule for the estimation of ∆Sb. The normal boiling
point is calculated as a ratio of the estimated ∆Hb to ∆Sb.
Theoretical Background
The normal boiling point (Tb), i.e., the boiling point at 1 atm
of a compound, is defined as the temperature at which the vapor
pressure of its liquid phase equals 1 atm. It is an outcome of
various molecular properties that affect the tendency of a
molecule to escape from the liquid surface. The enthalpy of
boiling and the entropy of boiling are the change in the
respective properties associated with the vaporization of the
liquid at its Tb. At the boiling point, the free energy of transition
is equal to zero and the three properties are related as
Tb ) ∆Hb/∆Sb (1)
The entropy of boiling is a measure of the increase in
randomness of a system upon boiling. According to Boltzmann’s
statistical definition, the entropy of boiling is related to the
relative probabilities of the existence of the gas and the liquid
states as
∆Sb ) R ln(ΩG/ΩL) (2)
where ΩL is the number of ways 1 mol of a material can be
found that would constitute the liquid phase and ΩG is the
number of ways those molecules can exist as a gas. It is
expressed as a sum of translational, rotational, and conforma-
tional components, i.e.,
 Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006 2857

∆Sb ) ∆SbTrans + ∆SbRot + ∆SbConf (3) Table 1. Summary of the Average Absolute Errors for the
Estimation of ∆Sb

The contribution of the translational component predominates AAEa

in eq 3. Boiling is associated with a large increase in the free data range Trouton’s
volume. As a consequence, the molar volume of the compound compounds n [J/(K mol)] eq XI rule
undergoes a large increase too, and the molecules gain a large rigid-non-H-bonding 287 69.7-131.7 4.5 4.3
amount of translational freedom upon boiling. For most liquids, flexible-non-H-bonding 863 47.4-137.0 4.3 4.4
the change in the free volume upon boiling is approximately rigid-H-bonding 40 78.6-127.5 7.3 12.5
flexible-H-bonding 132 62.4-133.4 7.2 13.8
equal to the volume of its gas. Since the volume of a gas is total data set 1322 47.4-137.0 4.7 5.6
almost constant under normal temperature-pressure conditions,
the change in the translational freedom of the molecules is nearly
a AAE ) ∑ (| experimental value - predicted value |)/n.
constant. This explains Trouton’s rule of constant entropy of liquid-phase enthalpy is more sensitive to temperature, ∆Cp,b
boiling of 88 J/(deg mol). The contributions of rotational and values are invariably negative. Because the effect of temperature
conformational freedom to the entropy of boiling are small since on ∆Cp,b has been shown to be small,15 ∆Cp,b is assumed to be
compounds have a large degree of rotational and conformational constant and equal to an average value calculated over (298 -
freedom in both the liquid and the gas phase. However, the Tb). Thus, eq 6 may be simplified as
effect of these contributions cannot be completely neglected.
Trouton’s rule works exceedingly well for the rigid noninter- ∆Hb ) ∆Hv + [∆Cp,b(Tb - 298)] (7)
acting molecules but should be modified to account for the
molecular properties such as flexibility and hydrogen-bonding The heat capacity change upon boiling has units of entropy
capability that may restrict rotational and conformational and depends on the same molecular parameters, flexibility, and
freedom in the liquid phase. hydrogen-bonding ability. It can be estimated using the follow-
The flexibility of a molecule arises from the ability of its ing equation,16
atoms to torsionally rotate about single bonds. A flexible
molecule has a greater degree of order in the liquid form because ∆Cp,b ) -56 - 4(τ) - 40(HBP) (8)
it tends to be partially aligned with its neighbors. Upon boiling,
the molecules tend to randomize and attain a higher conforma- where τ is the flexibility parameter of the compound and HBP
tional freedom resulting in an increase in entropy. Hydrogen is the hydrogen-bond parameter.
bonding restricts the rotational freedom of the molecules in the
liquid phase, whereas it has no effect over the large intermo- Experimental Section
lecular distance in the gas phase. As a consequence, hydrogen-
Estimation of the Entropy of Boiling. The equation for
bonding compounds typically have a higher entropy of boiling.
estimation of entropy of boiling is obtained by the multiple linear
Thus, the entropy of boiling may be estimated more accurately
regression (SPSS version 10) of the experimental entropy data
using the following equation:
using the flexibility parameter (τ) and the hydrogen-bond
∆Sb ) constant + effect of flexibility + parameter (HBP) as independent variables. These parameters
are defined below. The equation includes an intercept that
effect of hydrogen bonding (4)
represents the ∆Sb value for rigid, non-hydrogen-bonding
The molar enthalpy of vaporization at the boiling point compounds.
depends on the amount of energy required to vaporize 1 mol of Flexibility Parameter (τ). The flexibility parameter is
the liquid at its Tb. The nature of the functional groups calculated using the equation proposed by Dannenfelser and
constituting the molecule determines the strength of the Yalkowsky,17
intermolecular interactions in the liquid state. The enthalpy of
boiling is a function of the strength of these interactions and is τ ) (SP3 + 0.5SP2 + 0.5ring - 1) (9)
related to the number and the type of groups comprising the where SP3 and SP2 are the total number of nonring, nonterminal
molecule. Thus, it is reasonable to estimate ∆Hb using a group sp3 and sp2 atoms. Ring indicates the number of independent
contribution approach, single, fused, or conjugated ring systems in the molecule. Since

∑nibi
terminal atoms and sp hybrid atoms do not contribute to
∆Hb ) (5) flexibility, they are not counted. The rotation of hydrogen atoms
is also ignored. Aliphatic cyclic groups are counted as single-
where ni is the number of times a group appears in the
ring systems. Compounds with a negative value for τ are
compound and bi is its contribution to the enthalpy of boiling.
assigned a value of zero.
The experimental value of the enthalpy of vaporization at
Hydrogen-Bond Parameter (HBP). The effect of hydrogen
298 K (∆Hv) is more commonly available. Our data indicates
bonding was considered as a function of the number of different
that, although ∆Hv values may be more accurate as the
hydrogen-bonding groups [-OH, -COOH, and -NH (including
measurements are performed at lower temperature, these values
-NH and -NH2)] present on the molecule. The HBP is
are less constant than ∆Hb values. Thus, in this study, a group
calculated using the equation proposed by Sanghvi and
contribution scheme is developed for the estimation of ∆Hb
Yalkowsky:16
instead of ∆Hv. The two values are related by the following
equation,
HBP ) x[(#OH) + (#COOH) + 0.0625(#NH)] (10)
∆Hb ) ∆Hv + ∫298 ∆Cp,b dT
Tb
(6) where # is the number of respective groups (aliphatic or
aromatic).
where the value of ∆Cp,b is the difference between the enthalpy- Estimation of the Enthalpy of Boiling. The compounds were
temperature slopes of the gas phase and the liquid phase. Since fragmented using the group breakdown scheme (Table 2)
2858 Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006

Table 2. Group Values (bi) for the Enthalpy of Boiling (kJ/mol)a

groups bi(X) bi(Y) bi(YY) groups bi(X) bi(Y) bi(YY)
Carbon
sCH3 11.006 10.501 sCH2s 2.088 1.658 1.646
sCH< -7.169 -8.028 -8.860 >C< -16.722 -17.780 -44.349
dCH2 10.429 dCHs 2.41 2.255
dC< -5.839 -4.770 -9.438 dCH 9.124
dCs 3.152 4.130 dCd 1.852
sCsar -3.139 >C<bp -3.844
sCHar 5.267 >C<br -0.029
>CHsfus -1.084 >C<fus -2.033
>Cdfus 7.28 >CH2ring 4.606
>CHsring -4.064 >CHdring 4.396
>C<ring -14.345 dC<ring -4.072
ring-3 8.832 ring-4 6.845
ring-5 5.152 ring->5 2.742
Oxygen
1° OH 22.487 21.176 2° OH 20.921
3° OH 20.124 sOs 2.061 2.333 0.304
sOsar 5.785 sOsring 5.855
Oxygen and Carbon
sCHO 16.365 15.263 sCOs 6.826 5.589
sCOOH 30.100 29.191 sCOO 6.936 5.153
sHCOO 16.039 sCOOCO 13.415
sOCHO 2.942 HCOOH 38.117
sCOsring 10.047 sCOOsring 20.21
sCOOCOsring 27.451 sCOCl2 24.464
Nitrogen
1° NH2 15.222 17.329 2° NH2 14.051
3° NH2 12.508 sNHs 4.347 6.943
>Ns -7.454 -4.190 -7.911 dNs 9.323
sNdNs 3.07 sNHNH2 22.332
>NNH2 8.48 sNHNHs 10.822
>NNHs -6.417 sNHsar 15.505
sNsar 6.925 sNNsar 20.780
sNHsring 9.713 >Nsring -3.801
>PN3 -28.791 sNCBr 21.093
Nitrogen and Carbon
sCN 19.391 17.084 CNCN 21.907
HCN 26.013 sNCN ar -4.358
Nirogen and Oxygen
sNO2 19.835 17.529 sONO2 18.262
sNOsar 16.343
Nitrogen, Carbon, and Oxygen
sCONH 29.915 sCON 4.618
sNCHO 15.125 sNCO 16.992
sCONHsring 28.038 sCON<ring 11.349
sOCdNsring 8.447
Sulfur
sSH 15.308 15.385 sSs 5.478 3.786
sSSs 11.324 sSsar 10.41
sSsring 10.729
Sulfur and Carbon
sSCSs 27.77
Sulfur and Oxygen
sSO2s 12.539 18.856 sSOs 19.192
sSO3s 11.925
Sulfur, Carbon, and Oxygen
sOCSs 19.384
Sulfur, Carbon, and Nitrogen
sNCSs 22.754
Phosphorus and Oxygen
PO4 6.21
Phosphorus, Oxygen, and Sulfur
PO2S 0.668 PO2S2 -10.016
PO3S -8.783
Halogens
sF 10.61 8.265 sCl 13.714 12.139
sBr 15.435 14.115 sI 18.069 16.236
Proximity Effect
IHB-5 1.128 IHB-6 0.396
IHB-7 1.966 G-2 -2.242
G-3 -5.469 G-4 -9.318
a (X): The fragment is attached to singly bonded groups; (Y): the fragment is attached to one doubly or triply bonded group; and (YY): the fragment

is attached to two or more doubly or triply bonded groups. ar: aromatic; bp: atoms that are part of two aromatic rings; br: atoms that are part of more than
one aromatic rings; ring: atoms that are part of an aliphatic ring system; and ring- 3,4,5,>5: three, four, five, or more than five-membered aliphatic ring
systems, respectively. 1°: Primary aliphatic; 2°: secondary aliphatic; 3°: tertiary aliphatic; IHB-5,6,7: five-, six-, or seven-membered ring systems, respectively,
formed due to the formation of intramolecular hydrogen bonding. G-2,3,4: Carbons bound to two, three, or four halogens, respectively. Italicized values are
based on <5 occurrences.

proposed by Jain.19 This scheme takes into account the effect
of individual groups and their proximity on the heat of transition.
For describing the structure of compounds used in this study,
132 group values were required. This includes nine new groups
that were defined to describe the structure of some compounds
that are not covered by the scheme of Jain et al. The coefficients
of the groups for the estimation of enthalpy of boiling were
obtained by multiple linear regression (SPSS version 10) of the
experimental ∆Hb values.
Data. The experimental ∆Hv values for 1322 compounds
were obtained from Chickos and Acree.18 These compounds
were selected as the enthalpy measurements were performed at
298 K ((5 K). The experimental ∆Hb* values for these
compounds were calculated using eq 7. The experimental Tb
values for the compounds were obtained from the literature.
The experimental ∆Sb values were calculated as a ratio of ∆Hb*
and Tb. These values were used to develop the model for the
estimation of ∆Sb. The apparent experimental ∆Hb values were
obtained by multiplying the estimated ∆Sb and experimental
Tb values. These values were used to develop the model for the
estimation of ∆Hb.
Estimation of the Boiling Point. The boiling points of the
compounds were calculated by dividing the estimated ∆Hb
values by the respective estimated ∆Sb values.
Results and Discussion
Entropy of Boiling. On the basis of the statistical analysis,
the following equation was obtained for the estimation of ∆Sb:
∆Sb ) 87 + 0.35(τ) + 15(HBP) (11)
The average absolute error of the estimation is 4.7 J/(K mol),
corresponding to 5.2%. Table 1 summarizes the results obtained
using eq 11. The compounds have been divided into four
subsets: rigid-non-hydrogen-bonding; flexible-non-hydrogen-
bonding; rigid-hydrogen-bonding; and flexible-hydrogen-
bonding. For comparison, the results obtained using Trouton’s
rule are included in the table.
The table demonstrates the general applicability of Trouton’s
rule, particularly of rigid-non-hydrogen-bonding compounds.
However, the errors associated with flexible compounds are
slightly lower, and those for hydrogen-bonding compounds are
substantially lower with eq 11. The intercept of 87 J/(K mol) is
very close to Trouton’s constant entropy of boiling [88 J/(K
mol)], which accounts for the gain in the translational freedom
upon boiling.
The effect of increase in conformational and rotational
freedom cannot be totally neglected. These motions are some-
what restricted in the liquid phase, particularly for flexible
molecules. Intermolecular hydrogen bonding also restricts
molecular rotations in the liquid state. These restrictions are
relieved upon boiling, since the likelihood of hydrogen bonding
is negligible in the gas phase. Intuitively, the effect of dif-
ferent hydrogen-bonding groups on the entropy of boiling
depends on their strength. This is reflected in eq 10 which is
used to calculate HBP, where the coefficients of -COOH
and -OH groups are larger than that of an -NH group, since
the former are stronger hydrogen-bonding groups than the
latter. Since the -SH group is a very weak hydrogen-bonding
group, its effect on the entropy of boiling is insignificant. The
effect of hydrogen bonding increases with the number of such
groups, but this increase is not linear. The square root term in
eq 10 accounts for the fact that the formation of the first
hydrogen bond imposes geometric restrictions on the molecule
Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006 2859
Table 3. Summary of the Average Absolute Errors for the
Estimation of ∆Hb
compounds n data range (kJ/mol) AAEa
rigid-non-H-bonding 287 9.7-48.5 1.0
flexible-non-H-bonding 863 21.6-60.3 0.8
rigid-H-bonding 40 24.2-50.5 0.8
flexible-H-bonding 132 26.6-64.0 0.7
total data set 1322 9.7-64.0 0.8
a AAE ) ∑ (|(experimental value - predicted value)|)/n.
Figure 1. Estimated versus experimental boiling point (K).
to reduce the feasibility of the second hydrogen-bond forma-
tion. Molecules containing only hydrogen-bond acceptor groups
and no donor groups cannot undergo hydrogen-bond forma-
tion. Thus, the presence of groups such as carbonyl, nitro, or
halo does not appear to affect the entropy term. A mathemati-
cally significant effect of such groups in the estimation was
not observed.
Enthalpy of Boiling. The group values for the estimation of
the enthalpy of boiling are given in Table 2. The summation of
these values is used to calculate the total enthalpy for each
compound using eq 5.
The group breakdown scheme of Jain19 was proposed
originally for estimating the enthalpy of melting. An addition
of nine new groups was made to describe the structures of some
compounds that were not covered by the original scheme. The
average absolute error associated with the estimation is 0.83
kJ/mol, which correspond to 2.3%. These results are summarized
in Table 3. The considerable accuracy obtained with the
estimation of enthalpy of boiling using this scheme indicates
that the influence of a group on the process of melting and
boiling is qualitatively similar. However, the coefficients for
the estimation of enthalpy of boiling are generally larger than
those for the estimation of enthalpy of melting.
Normal Boiling Point. The estimated boiling points for the
compounds used in this study were calculated by incorporating
eqs 5 and 11 into eq 1:
Tb ) [ ∑nibi]/[87 + 0.35(τ) + 15(HBP)] (12)
The average absolute error of estimation is 9.3 K, corresponding
to 2.3%. A correlation coefficient (r2) of 0.98 was obtained with
a standard deviation of 9.8 K. A plot of the predicted versus
the experimental boiling points is given in Figure 1.
It is noticed that slightly higher negative errors were associ-
ated with high-boiling compounds. The systematic overpredic-
tion for such compounds may be due to the underestimation of
entropy of boiling. Also for extremely high-boiling compounds,
the likelihood for thermal decomposition exists at temperatures
near their boiling points.
The results obtained for the estimation of the boiling points
are presented in Table 4. The proposed model performs well,
2860 Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006

Table 4. Summary of the Average Absolute Errors for the

Estimation of Tb
∆Hb ) ∑nibi ) 1(XCH3) + 1(XCH2) + 1(YCH) +
1(XCHd) + 1(CH2d) + 1(2° OH)
compounds n data range (K) AAEa
rigid-non-H-bonding 287 111.6-557.5 11.4 ) (11.006) + (2.088) + (-8.028) + (2.41) +
flexible-non-H-bonding 863 247.0-639.0 8.9 (10.429) + (20.921) ) 38.83 kJ/mol
rigid-H-bonding 40 266.7-518.0 8.1
flexible-H-bonding 132 292.0-581.5 7.1 Predicted Tb ) ∆Hb/∆Sb )
total data set 1322 111.6-639.0 9.3
38.83 × 1000/102.53 ) 378.7 K
a AAE ) ∑ (| (experimental value - predicted value) |)/n.
Absolute error ) 8.8 K (2.2%)
Table 5. Cross-Validation Results of the Proposed Model
training set test set (b) N,N-Dimethylbenzylamine.
cross validation n AAEa n AAEa
round 1 1190 9.4 K 129 11.1 K
round 2 1190 9.3 K 130 9.9 K
round 3 1190 9.6 K 128 10.1 K
a AAE ) ∑ (| (experimental value - predicted value) |)/n.

especially for the hydrogen-bonding compounds. It should be

mentioned that, although the hydrogen-bonding term appears
directly in the entropy term, its effect is much higher in the
enthalpy-of-boiling calculation. This is in accordance to the fact
Experimental Tb: 456.0 K
that hydrogen-bonding compounds have a tendency to boil at
higher temperatures than their non-hydrogen-bonding counter- SP3: 2, SP2: 0, ring: 1
parts.
∆Sb ) 87 + 0.35(τ) + 15(HBP)
Cross-Validation
) 87 + 0.35 (2 + 0 + 0.5 - 1) ) 87.53 J/(K mol)
The validity of the proposed model was tested by cross-valida-
tion. For this purpose, the entire data set was randomized and
the first 10% of compounds were used as the test set. The
∆Hb ) ∑nibi ) 2(XCH3) + 1(YCH2) + 1(XN) +
remaining 90% of the compounds (n ) 1190) were used as the 5(CHar) + 1(Car)
training set to generate the coefficients for the estimation. The ) 2(11.006) + (1.658) + (-7.454) + 5(5.267) +
results for cross-validation are given in Table 5. The average (-3.139) ) 39.41 kJ/mol
absolute errors for the training and test sets are comparable for
all three rounds. The paired T-test indicates that the experimental Predicted Tb ) ∆Hb/∆Sb )
and the predicted boiling points for the test compounds were
(39.41 × 1000)/87.53 ) 450.3 K
statistically not different (R ) 0.05) for all three rounds.

Conclusion
Absolute error: 5.7 K (1.3%)
The proposed semiempirical model enables a simple, accurate, Supporting Information Available: The experimental and
and widely applicable method for estimation of the normal the estimated values for the normal boiling point along with
boiling point of organic compounds based on their chemical the absolute errors are available for all the organic compounds
structure. The enthalpy of boiling can be estimated using the used in this study. This material is available free of charge via
proposed group contribution values. The entropy of boiling can the Internet at http://pubs.acs.org.
be estimated using a modified Trouton’s rule. The normal
boiling point is than calculated as the ratio of the two values. Literature Cited
(1) Yalkowsky, S. H.; Dannenfelser, R. M.; Myrdal, P.; Simamora, P.
Examples Unified Physical Property Estimation Relationship (UPPER). Chemosphere
1994, 28, 1657-1673.
(a) 1-penten-3-ol. (2) Fisher, C. H. Boiling Point Gives Critical Temperature. Chem. Eng.
1989, 96, 157-158.
(3) Satyanarayana, K.; Kakati, M. C. Note: Correlation of Flash Points.
Fire Mater. 1991, 15, 97-100.
(4) Sladkov, B. Estimation of Molar Volume of Inorganic Liquids at
Boiling Points. J. Appl. Chem. 1991, 64, 2273.
(5) Herberger, K. Discrimination between Linear and Non-Linear Models
Describing Retention Data of Alkylbenzene in Gas-Chromatography.
Chromatographia 1990, 29, 275.
(6) Rucker, G.; Rucker, C. On topological indices, boiling points, and
Experimental Tb: 387.5 K cycloalkanes. J. Chem. Inf. Comput. Sci. 1999, 39, 788-802.
(7) Dearden, J. C. Quantitative Structural-Property Relationship for
Prediction of Boiling Point, Vapor Pressure, and Melting Point. EnViron.
SP3: 2, SP2: 1, ring: 0, #(OH): 1 Toxicol. Chem. 2003, 22, 1696-1709.
∆Sb ) 87 + 0.35(τ) + 15(HBP) (8) Joback, K. G.; Reid, R. C. Estimation of pure-component properties
from group contributions. Chem. Eng. Commun. 1987, 57, 233-243.
(9) Constantinou, L.; Gani, R. New group contribution method for
) 87 + 0.35(2 + 0.5 + 0 - 1) + estimating properties of pure compounds. AIChE J. 1994, 40, 1697-
15(1) ) 102.53 J/(K mol) 1710.

(10) Stein, S. E.; Brown, R. L. Estimation of Normal Boiling Point from
Group Contribution. J. Chem. Inf. Comput. Sci. 1994, 34, 581-587.
(11) Nannoolal, Y.; Rarey, J.; Ramjugernath, D.; Cordes, W. Estimation
of Pure Component Properties. Part 1. Estimation of Normal Boiling Point
of Non-Electrolyte Organic Compounds via Group Contribution and Group
Interactions. Fluid Phase Equilib. 2004, 226, 45-63.
(12) Wessel, M. D.; Jurs, P. C. Prediction of Normal Boiling Points of
Hydrocarbons from Molecular Structure. J. Chem. Inf. Comput. Sci. 1995,
35, 68-76.
(13) Basak, S. C.; Gute. B. D.; Grunwald, G. D. A Comparative Study
of Topological and Geometrical Parameters in Estimating Normal Boiling
Point and Octanol/Water Partition Coefficient. J Chem. Inf. Comput. Sci.
1996, 36, 1054-1060.
(14) Kolska, Z.; Ruzicka, V.; Gani, R. Estimation of the Enthalpy of
Vaporization and the Entropy of Vaporization for Pure Organic Compounds
at 298.15 K and at Normal Boiling Temperature by a Group Contribution
Method. Ind. Eng. Chem. Res. 2005, 44, 8436-8454.
Ind. Eng. Chem. Res., Vol. 45, No. 8, 2006 2861
(15) Myrdal, P. B.; Yalkowsky, S. H. Estimating Pure Component Vapor
Pressures of Complex Organic Molecules. Ind. Eng. Chem. Res. 1997, 36,
2494-2499.
(16) Sanghvi, R.; Yalkowsky S. H. Estimation of Heat Capacity of
Boiling for Organic Compounds. Ind. Eng. Chem. Res. 2006, 45, 451-453.
(17) Dannenfelser, R. M.; Yalkowsky, S. H. Predicting the Total Entropy
of Melting: Application to Pharmaceutical and Environmentally Relevant
Compounds. J. Pharm. Sci. 1999, 88, 722-724.
(18) Chickos, J.; Acree, W. E. Enthalpies of Vaporization of Organic
and Organometallic Compounds 1880-2002. J. Phys. Chem. Ref. Data
2003, 32, 519-878.
(19) Jain, A. Ph.D. Thesis, University of Arizona, Tucson, AZ, 2005.
ReceiVed for reView November 17, 2005
ReVised manuscript receiVed February 15, 2006
Accepted February 16, 2006
IE051277G